WO2008133338A1 - Elément conducteur - Google Patents

Elément conducteur Download PDF

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Publication number
WO2008133338A1
WO2008133338A1 PCT/JP2008/058232 JP2008058232W WO2008133338A1 WO 2008133338 A1 WO2008133338 A1 WO 2008133338A1 JP 2008058232 W JP2008058232 W JP 2008058232W WO 2008133338 A1 WO2008133338 A1 WO 2008133338A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive member
spacer
particles
particle size
conductive
Prior art date
Application number
PCT/JP2008/058232
Other languages
English (en)
Inventor
Toru Sato
Shingo Eguchi
Noriaki Oguri
Original Assignee
Canon Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Kabushiki Kaisha filed Critical Canon Kabushiki Kaisha
Priority to EP08740917A priority Critical patent/EP2143113A1/fr
Priority to US12/282,378 priority patent/US20100231114A1/en
Publication of WO2008133338A1 publication Critical patent/WO2008133338A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H01J29/864—Spacers between faceplate and backplate of flat panel cathode ray tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J31/00—Cathode ray tubes; Electron beam tubes
    • H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
    • H01J31/10—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes
    • H01J31/12—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes with luminescent screen
    • H01J31/123—Flat display tubes
    • H01J31/125—Flat display tubes provided with control means permitting the electron beam to reach selected parts of the screen, e.g. digital selection
    • H01J31/127—Flat display tubes provided with control means permitting the electron beam to reach selected parts of the screen, e.g. digital selection using large area or array sources, i.e. essentially a source for each pixel group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00—Electron emission display panels, e.g. field emission display panels
    • H01J2329/86—Vessels
    • H01J2329/8625—Spacing members
    • H01J2329/864—Spacing members characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00—Electron emission display panels, e.g. field emission display panels
    • H01J2329/86—Vessels
    • H01J2329/8625—Spacing members
    • H01J2329/8645—Spacing members with coatings on the lateral surfaces thereof

Definitions

  • the present invention relates to a spacer, which is a construction element of an image display apparatus having an electron-emitting device, a conductive member suitable for the spacer, and an image display apparatus using the conductive member as the spacer.
  • a flat display having an electron-emitting device as disclosed in Patent Document 1, has an atmosphere pressure-resistance maintenance structure called a spacer or rib to maintain a high vacuum inside thereof.
  • FIG. 7 is a sectional schematic diagram of an image display apparatus having many electron-emitting devices.
  • reference numeral 15 is a rear plate
  • reference numeral 16 is a side wall
  • reference numeral 17 is a face plate.
  • An airtight vessel is formed by the rear plate 15, the side wall 16, and the face plate 17.
  • a spacer 20b which is an atmosphere pressure-resistance maintenance structure of the airtight vessel, has a low resistance film 70.
  • the low resistance film 70 is connected to a wiring 13 via a conductive flit 78.
  • An electron-emitting device 12 is formed on the rear plate 15.
  • a phosphor film 18 and a metal back 19 are formed on the face plate 17.
  • the metal back 19 is provided to improve light availability by specular reflection of a portion of light emitted from the phosphor film 18, to protect the phosphor film 18 from collision of anions, and to be used as an electrode for applying a voltage to accelerate an electron beam.
  • the metal back 19 is also provided for use as a conductive path of excited electrons in the phosphor film 18.
  • FIG. 7 shows a charged state of the spacer.
  • the spacer is charged (FIG. 7: positive charging) by collision of a portion of electrons emitted from an electron source near the spacer.
  • thickness of the low resistance film 70 of a spacer 20a having no antistatic film 72 is drawn more thickly than that of the low resistance film 70 in contact with the antistatic film 72 of the spacer 20b.
  • Patent Document 2 discloses, as a technology to effectively suppress charging on the surface of a spacer, a technology to make an effective secondary electron emission coefficient smaller by providing unevenness on the surface of a glass substrate as a spacer than when the surface of the spacer is smooth.
  • Patent Document 1 Japanese Patent Application Laid- Open Publication No. 10-284286
  • Patent Document 2 Japanese Patent Application Laid- Open Publication No. 2001-143620 (USP6494757)
  • the distribution of temperature in the spacer 20b becomes nonuniform due to a variety of factors, the distribution of resistance of the antistatic film 72 also becomes nonuniform due to resistance temperature characteristics of the antistatic film 72.
  • the distribution of resistance causes fluctuations of a discharging function.
  • images near the spacer 20b are disturbed by nonuniform distribution of temperature inside the panel surface.
  • the nonuniform distribution of temperature inside the panel surface is caused by a difference of temperature between the face plate 17 and the rear plate 15.
  • an antistatic film shown in a conventional example is formed by a film formation method using a vacuum apparatus such as a sputtering method and therefore, it is difficult to reduce manufacturing costs.
  • An object of the present invention is to provide a conductive member that can be produced at low costs and has excellent resistance temperature characteristics, a spacer made of the conductive member, and an image display apparatus using the spacer.
  • a first aspect in accordance with the present invention is a conductive member comprising a base material and conductive particles whose conductivity is larger than that of the base material dispersed in the base material, the conductive particles are dispersed in such a way that activation energy of the conductive member is 0.3 eV or less and volume resistivity of the conductive member is 10 5 ⁇ cm or more.
  • the conductive particles are preferably dispersed in the base material in such a way that Ea (activation energy) of the conductive member is 0.2 eV or less.
  • the conductive particles are preferably dispersed in such a way that volume resistivity of the conductive member is 10 8 ⁇ cm or more.
  • a particle diameter of the conductive particles preferably is not less than 0.5 nm and not more than 50 ⁇ m.
  • the conductive particles preferably have a volume fraction to the whole conductive member of 50 vol% or less .
  • the conductive particles are preferably formed of at least one metal selected from gold, platinum, silver, palladium, ruthenium, rhodium, osmium, and iridium.
  • a second aspect in accordance with the present invention is a spacer arranged between a first substrate and a second substrate in an image display apparatus comprising an airtight vessel having the first substrate having an electron source and the second substrate having an image display member opposite to the electron source, wherein the spacer is the conductive member of the present invention.
  • a third aspect in accordance with the present invention is an image display apparatus comprising an airtight vessel having a first substrate having an electron source and a second substrate having an image display member opposite to the electron source and a spacer arranged between the first substrate and the second substrate, and the spacer is the conductive member of the present invention.
  • a conductive member of the present invention When a conductive member of the present invention is used as a spacer of an image display apparatus, resistance of the conductive member changes only slightly when the temperature changes and therefore, a disturbance of display images caused by nonuniform distribution of temperature inside an airtight vessel can be controlled to a minimum.
  • the conductive member is produced without a vacuum film formation process and thus, can be provided as a low- cost spacer.
  • a conductive member of the present invention can also be used as a conductive control member used for a developing roller, a transfer roller, a cleaning blade, a cleaning roller, a feed roller or the like in an electrophotographic apparatus such as a copying machine and a printer.
  • FIG. IA is a diagram exemplifying a conductive member according to the present invention.
  • FIG. IB is a schematic diagram showing an observation result of an arbitrary A-A' section of the conductive member according to the present invention by TEM or SEM.
  • FIG. 2 is a perspective view showing an example of an image display apparatus according to the present invention by cutting out a portion of a display panel.
  • FIG. 3 is an Arrhenius plot showing resistance temperature characteristics of the conductive member according to the present invention.
  • FIG. 4 is a diagram illustrating a beam movement magnitude ⁇ L developing as a disturbance of image due to an influence of a spacer when there is a difference between a temperature of a face plate and that of a rear plate in the image display apparatus according to the present invention.
  • FIG. 5 is a diagram illustrating, in the image display apparatus according to the present invention, activation energy Ea of the conductive member and an allowable temperature difference ⁇ T between the face plate and rear plate of the image display apparatus with respect to a beam movement magnitude perceivable as a disturbance of image.
  • FIG. 6 is a diagram illustrating a relationship between the particle size of conductive particles and activation energy in the conductive member according to the present invention.
  • FIG. 7 is a sectional schematic diagram of an image display apparatus having an electron-emitting device for illustrating a mechanism of charging in a spacer according to the present invention.
  • FIG. 8 is a diagram illustrating the beam movement magnitude ⁇ L manifesting itself as a disturbance of image due to the influence of the spacer according to the present invention.
  • FIG. 9 is a diagram showing relationships between a particle size ratio (coarse-particle/fine-particle) during mold filling and a filling ratio in a making process of the conductive member according to the present invention.
  • FIG. 10 is a table showing evaluation results of a spacer.
  • An object of the present invention is to reduce a disturbance of images near a spacer caused by a difference of temperature between the face plate and rear plate or the like. More specifically, the disturbance of images is caused by nonuniform distribution of temperature in the spacer.
  • a difference of temperature between the face plate and rear plate is controlled, a difference of temperature between the face plate and rear plate of several degrees may partially occur depending on an outside environment such as an installation location of a display apparatus.
  • the distribution of temperature in the spacer may fluctuate by several degrees depending on an operating state of the display apparatus .
  • the phenomenon is caused in the following manner.
  • electrons emitted from an electron-emitting device on the rear plate generate reflected electrons on the face plate. These reflected electrons are irradiated to the spacer. More of these reflected electrons are irradiated to the side of the face plate (face plate side) of the spacer than the side of the rear plate (rear plate side) of the spacer. Also, energy of reflected electrons irradiated to the face plate side of the spacer is larger than that of reflected electrons irradiated to the rear plate side of the spacer.
  • the temperature on the face plate side of the spacer is a little higher than that on the rear plate side of the spacer. Therefore, even if the temperature of the face plate and that of the rear plate are controlled, the distribution of temperature in the spacer fluctuates by several degrees depending on the outside environment and operating environment. Thus, a spacer in which nonuniform distribution of resistance does not occur is demanded even if such nonuniform distribution of temperature occurs.
  • a conductive member having a plurality of conductive particles dispersed in an insulating base material as a conductive spacer.
  • electric resistivity caused by temperature changes can be reduced more by controlling activation energy (Ea) and volume resistivity (p) in certain electric field intensity and temperatures ranges.
  • a conductive member according to the present invention is formed by dispersing conductive particles whose conductivity is larger than that of an insulating base material .
  • Conductive particles are dispersed in such a way that Ea of the conductive member is 0.3 eV or less and volume resistivity thereof is 10 5 ⁇ cm or more. If a dispersion state of conductive particles is such that Ea of the conductive member exceeds 0.3 eV, electric resistance of the spacer partially fluctuates due to nonuniform distribution of temperature in an airtight vessel caused by a difference of temperature between a first substrate and a second substrate when the conductive member is used as a spacer. Thus, an influence thereof affects the display.
  • a more suitable dispersion state for a conductive member according to the present invention is one in which Ea of the conductive member is 0.2 eV or less and/or volume resistivity thereof is 10 8 ⁇ cm or more .
  • powder of an insulating base material and that of conductive particles are each prepared.
  • a powder manufacturing means is not particularly limited. Such powder is obtained by a physical method such as a crusher, a laser type fine-particle manufacturing machine, and an induction heating fine-particle manufacturing machine, or a chemical method such as an aerosol atomization method and a thermal decomposition method. Such powder is classified by a sieve, a dry classifier, a wet classifier or the like to obtain a desired particle size.
  • Powder of the base material and that of conductive particles are measured by various composition ratios and then mixed.
  • powder of glass and that of gold particles are mixed.
  • a mixing means is not particularly limited. Such powder is mixed, for example, by a ball mill. Mixing of such powder performs in a non-oxidation atmosphere such as a nitrogen gas and an Ar gas .
  • the mixed powder is pre-sintered in an inert gas such as a nitrogen gas and an Ar gas atmosphere, or in a vacuum.
  • the mixed powder may also be pre-sintered in a reduction atmosphere such as hydrogen gas.
  • the temperature of pre-sintering is suitably 800 0 C or more and 1500°C or less.
  • a mixed solid body generated by pre-sintering is crushed.
  • a crushing means is not particularly limited.
  • the mixed solid body is crushed by a ball mill. Crushing of the mixed solid body performs in a non-oxidation atmosphere such as a nitrogen gas and an Ar gas.
  • Mixed powder obtained after the mixed solid body being crushed is classified by a sieve, a dry classifier, a wet classifier or the like to obtain powder of a required particle size.
  • powder whose particle size is large is called a coarse particle and that whose particle size is small is called a fine particle.
  • the mixed powder obtained in the crushing process is filled into a mold in an inert gas atmosphere such as a nitrogen gas and an Ar gas, or in a vacuum.
  • An inert gas atmosphere such as a nitrogen gas and an Ar gas, or in a vacuum.
  • a plurality of particles (coarse particles and fine particles) having different particle sizes obtained by classification is selected and the particles (coarse particles and fine particles) are filled by various compounding ratios (mass ratios) .
  • Compaction is performed by providing vibration to the mold so that fine particles having a smaller particle size are flow into voids formed by among coarse particles having a larger particle size.
  • the particle size ratio of coarse particles and fine particles in mixed powder is suitably 100 or less.
  • the particle size ratio is preferably 10 ⁇ particle size ratio ⁇ 20.
  • the filling ratio can be improved by controlling the compounding ratio and particle size ratio in mixed powder. Further, conductive particles can uniformly be dispersed. [0028] (6) Sintering
  • a sintered body is obtained by pressure-sintering mixed powder filled into the mold, in an inert gas atmosphere such as a nitrogen gas and an Ar gas, or in a vacuum.
  • the mixed powder may also be pressure- sintered in a reduction atmosphere such as hydrogen gas.
  • Hot pressing is preferably used for pressure sintering.
  • Mixed powder is formed into a predetermined thickness or shape, and sintering is preferably performed under conditions of pressure of 1 MPa or more and 2 MPa or less and temperature of 800°C or more and 1500°C or less.
  • the mixed powder is thereby made a conductive member.
  • the conductive member is thereby made a spacer of an image display apparatus according to the present invention.
  • the shape of the spacer is not limited to a tabular shape (plate like shape) .
  • the shape of the spacer may also be cruciform, L-shaped, columnar, or an electron beam passage portion having a hole.
  • a base material of a conductive member the material in particular is not limited.
  • glass is preferably used as the base material.
  • Conductive particles whose electrical conductivity is higher than that of the base material may be used as the conductive particles of the present invention.
  • At least one metal selected, for example, from gold, platinum, silver, palladium, ruthenium, rhodium, osmium, and iridium is preferably used as a material of the conductive particles .
  • FIG. 2 is a perspective view of a display panel in an image display apparatus according to the present invention.
  • FIG. 2 shows the display panel by cutting out a portion thereof to show an internal structure of the display panel.
  • reference numeral 15 is a rear plate
  • reference numeral 16 is a side wall
  • reference numeral 17 is a face plate.
  • An airtight vessel to maintain a vacuum of an inner part of the display panel is formed by the rear plate 15, the side wall 16, and the face plate 17.
  • the first substrate and second substrate according to the present invention correspond each to the rear plate or the face plate.
  • joint parts of each member need to have sufficient strength and airtightness.
  • joint parts need to be sealed. Sealing is performed, for example, by applying frit glass to a joint part and then, sintering the frit glass at 400°C or more and 500°C or less for 10 minutes or longer in the atmosphere or in a nitrogen atmosphere. A method of evacuating the airtight vessel to a vacuum will be described later.
  • the inner part of the airtight vessel is maintained in a vacuum of about 10 ⁇ 4 [Pa] .
  • a spacer 20 is provided inside the display panel as an atmosphere pressure-resistance maintenance structure to prevent breakdown of the airtight vessel due, for example, to the atmosphere pressure or an unexpected impact.
  • the aforementioned conductive member having an insulating base material and conductive particles dispersed in the base material is used as the spacer 20.
  • the dispersion state of the conductive particles in the base material is controlled in such a way that Ea of the conductive member is 0.3 eV or less and volume resistivity thereof is 10 5 ⁇ cm or more.
  • N x M surface conduction electron-emitting devices 12 are formed on the substrate 11.
  • N and M are positive integers equal to or greater than 2.
  • the N x M surface conduction electron-emitting devices 12 are wired as a simple matrix type by connecting M row wiring 13 and N column wiring 14. A portion configured by the substrate 11, the electron- emitting devices 12, the row wiring 13, and the column wiring 14 is called an electron source substrate.
  • the phosphor film 18 is formed on the underside of the face plate 17.
  • the phosphor film 18 has a metal back 19, which is known in the field of CRT, provided on the surface on the side of the rear plate 15.
  • DxI to Dxm, DyI to Dyn, and Hv are terminals for electric connection having an airtight structure to electrically connecting the display panel and an electric circuit (not shown) .
  • DxI to Dxm are electrically connected to the row wiring 13 of the surface conduction electron-emitting devices.
  • DyI to Dyn are electrically connected to the column wiring 14 of the electron-emitting devices 12.
  • Hv is electrically connected to the metal back 19 of the face plate 17.
  • an exhaust pipe (not shown) and a vacuum pump are connected. Then, the inner part of the airtight vessel is evacuated to a vacuum by evacuating the airtight vessel using the vacuum pump to a vacuum of 10 "5 [Pa] or less. Subsequently, the exhaust pipe is sealed. At this point, a getter film (not shown) is formed at a predetermined position inside the airtight vessel immediately before or after sealing in order to maintain the degree of vacuum inside the airtight vessel.
  • the getter film is a film evaporated and formed at the predetermined position by heating a getter material containing Ba as a main component by using a heater or through high-frequency heating.
  • the inner part of the airtight vessel is maintained at the degree of vacuum 1 x ICT 3 Pa or more and 1 x 10 ⁇ 5 Pa or less by adsorbing action of the getter film.
  • a voltage is applied to each of the electron-emitting devices 12 via the ex-vessel terminals DxI to Dxm and DyI to Dyn. Electrons are thereby emitted from each of the electron-emitting devices 12.
  • the emitted electrons are accelerated by applying a high voltage of several hundred V to several kV to the metal back 19 via the ex-vessel terminal Hv. Then the emitted electrons before being caused to collide against an inner surface of the face plate 17.
  • the phosphor of each color in the phosphor film 18 is excited by collision of an electron beam. Accordingly, the phosphor of each color in the phosphor film 18 emits light. Thereby, an image is displayed.
  • the voltage applied to the electron- emitting devices 12 is about 12 to 16 [V] .
  • a distance d between the metal back 19 and the electron-emitting devices 12 is about 0.1 to 8 [mm].
  • the voltage between the metal back 19 and the electron-emitting devices 12 is about 0.1 to 12 [kV] .
  • a performance evaluation of the conductive member according to the present invention was performed. That is, an image evaluation was performed by mounting the conductive member in an image apparatus as a spacer and measuring the beam movement magnitude ⁇ L by the influence of the spacer. [ 0048 ]
  • a transparent film heater is attached to an outside surface of each of the rear plate 15 and the face plate 17 of the image display apparatus.
  • a difference of temperature between the face plate 17 and the rear plate 15 is caused by adjusting electric power provided to the transparent film heater attached to the rear plate 15 and that attached to the face plate 17 respectively.
  • the spacer 20 can be considered to have nonuniform distribution of temperature due to the difference of temperature between the face plate 17 and the rear plate 15.
  • the conductive member also has nonuniform distribution of resistance due to resistance temperature characteristics of the conductive member. The distribution of resistance manifests itself as fluctuations of the discharging function, leading to a disturbance of images near the spacer 20.
  • Resistance temperature characteristics of a conductive member according to the present invention will be described using the Arrhenius plot (1) .
  • Ea is used as an index of the quality of resistance temperature characteristics.
  • FIG. 3 shows an Arrhenius plot of resistance temperature characteristics of a conductive member. It is evident from FIG. 3 that a conductive member whose Ea is small has excellent resistance temperature characteristics that a resistance change with respect to a temperature change is small.
  • the discharging function of a conductive member according to the present invention was evaluated by image evaluation such as mounting the conductive member in an image display apparatus as a spacer and measuring the beam movement magnitude ⁇ L by the influence of the spacer.
  • the image display apparatus was installed in a dark room and a difference of temperature between the face plate and the rear plate was caused. Then, a CCD camera was installed at a location a predetermined distance apart from the panel surface to capture a display image.
  • the beam movement magnitude ⁇ L by the influence of the spacer was determined by calculating the beam position based on the captured image.
  • the beam movement magnitude ⁇ L due to a temperature difference ⁇ T can be controlled to a minimum when a conductive member whose Ea is small is used as a spacer.
  • FIG. 4 shows results thereof.
  • An image is displayed in an image display apparatus by causing an electron beam emitted from an electron-emitting device provided on the rear plate to collide against a phosphor film provided on the face plate.
  • a difference of temperature between the face plate and rear plate is caused depending on display images and driving conditions.
  • the difference of temperature results in temperature distribution in the spacer, which is made of a conductive member.
  • nonuniform distribution of resistance is created by resistance temperature characteristics of the conductive member.
  • the distribution of resistance manifests itself as fluctuations of the discharging function, leading to a disturbance of images near the spacer.
  • FIG. 5 shows a relationship between the allowable temperature difference between the face plate and rear plate and activation energy Ea for the movement magnitude ⁇ L ⁇ 0.01L when determined to be “not visible” in the sensory evaluation, and that between the allowable temperature difference between the face plate and rear plate and activation energy Ea for the movement magnitude ⁇ L ⁇ 0.03L when determined to be " visible, but not disturbing” in the sensory evaluation.
  • this result means that images are not disturbed if Ea ⁇ 0.3 eV even if temperature distribution of several degrees occurs in the spacer.
  • the volume resistivity p of the spacer is less than 10 5 ⁇ cm, a large current flows in the spacer even if Ea ⁇ 0.3 eV. Accordingly, the temperature of the whole spacer rises, leading to reduced resistance of the spacer. Thus, a so-called a thermal runaway may occur. In this case, there arises a problem that operations of the display apparatus become instable.
  • the spacer needs to have the volume resistivity p of 10 5 ⁇ cm or more and the activation energy Ea of 0.3 eV or less.
  • FIG. IA An arbitrary A-A 1 section of a conductive member 3 shown in FIG. IA was observed by a TEM (transmission electron microscope) or a SEM (scanning electron microscope) .
  • FIG. IB which is a schematic diagram, the conductive member 3 has a structure in which a plurality of conductive particles 1 having an average particle size (particle diameter) of 0.5 nm or more and 50 ⁇ i ⁇ or less is dispersed in a base material 2.
  • the average particle size is an average value of particle size of 20 conductive particles that obtained from an observation result of a section as shown in FIG. IB.
  • FIG. 6 shows a relationship between the particle size of conductive particles contained in the conductive member and activation energy (Ea) .
  • the average particle size is 0.5 nm or more, preferably 1 nm or more, it is easy to satisfy Ea ⁇ 0.3 eV. That is, if the average particle size takes a value described above, a conductive member having excellent resistance temperature characteristics that resistance changes only slightly when the temperature changes can be produced.
  • the ratio of conductive particles to the whole conductive member is preferably 50 vol% in terms of volume fraction. If the volume fraction exceeds 50 vol%, it is difficult to increase the volume resistivity p of the conductive member to 10 5 ⁇ cm or more. By using a conductive member whose volume fraction is 50 vol% or less as a spacer in an image display apparatus, a disturbance of images caused by the spacer can be made smaller. [0059] (Example 1)
  • Gold particles having the particle size of 0.5 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 800 0 C. The filling ratio of the conductive member was 96%.
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of gold particles was 0.5 nm.
  • volume resistivity of the conductive member was measured by applying a predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200°C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics.
  • the volume resistivity p of the conductive member was 1 x 10 8 ⁇ cm. The activation energy Ea was 0.3 eV.
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • the beam movement magnitude ⁇ L was 3% or less (0.03L or less). That is, when the temperature difference was 8 0 C or less, display images were good. Further, when the temperature difference between the face plate and rear plate was 3°C or less, the beam movement magnitude ⁇ L was 1% or less (0.01L or less) . That is, when the temperature difference was 3°C or less, display images were particularly good.
  • Gold particles having the particle size of 50 ⁇ m were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 1 MPa at 800°C. The filling ratio of the conductive member was 96%.
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM. The average particle size of gold particles was 50 ⁇ m.
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200°C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics. The volume resistivity p of the conductive member was 1 x 10 5 ⁇ cm. The activation energy Ea was 0.2 eV. [0067]
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • Gold particles having the particle size of 1 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 800°C. The filling ratio of the conductive member was 96%.
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of gold particles was 1 nm.
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/itim) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200°C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics.
  • the volume resistivity p of the conductive member was 1 x 10 8 ⁇ cm. The activation energy Ea was 0.2 eV.
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • Gold particles having the particle size of 0.5 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 8:2 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 800°C. The filling ratio of the conductive member was 78%. Many voids were present in the conductive member.
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of gold particles was 0.5 nm.
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200 0 C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics. The volume resistivity p of the conductive member was 1 x 10 5 ⁇ cm. However, the activation energy Ea was 0.4 eV. [0077]
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • Gold particles having the particle size of 0.5 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800 0 C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 5 ⁇ m were obtained. The particle size ratio of coarse particles to fine particles was set to 100.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 800°C. The filling ratio of the conductive member was 97%.
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of gold particles was 0.5 nm.
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200 0 C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics. The volume resistivity p of the conductive member was 1 x 10 5 ⁇ cm. However, the activation energy Ea was 0.4 eV. [0082]
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • Gold particles having the particle size of 100 ⁇ m were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 1 MPa at 800 0 C. The filling ratio of the conductive member was 96%.
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of gold particles was 100 ⁇ m.
  • Gold particles having the particle size of 0.5 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 80O 0 C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 800°C. The filling ratio of the conductive member was 96%.
  • the activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics.
  • the volume resistivity p of the conductive member was 1 x 10 3 ⁇ cm.
  • the activation energy Ea was 0.2 eV.
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • a predetermined voltage was applied between the face plate having a metal back and the rear plate having surface conduction electron-emitting devices to display images.
  • a current flowing through the spacer continued to increase. This is because of a phenomenon in which resistance of the conductive member decreases due to a temperature rise caused by electric power consumed by the spacer and the temperature continues to rise due to additional heating so that an overcurrent flows. This phenomenon is a so-called a thermal runaway.
  • Platinum particles having the particle size of 0.5 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 1500 0 C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre-sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ i ⁇ were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 1500°C. The filling ratio of the conductive member was 96%.
  • the average particle size of platinum particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of platinum particles was 0.5 nm.
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200°C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics. The volume resistivity p of the conductive member was 1 x 10 8 ⁇ cm. The activation energy Ea was 0.3 eV. [0093]
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • the beam movement magnitude ⁇ L was 3% or less (0.03L or less) . That is, when the temperature difference was 8 0 C or less, display images were good. Further, when the temperature difference between the face plate and rear plate was 3°C or less, the beam movement magnitude ⁇ L was 1% or less (0.01L or less) . That is, when the temperature difference was 3°C or less, display images were particularly good. [0095] (Example 5)
  • Platinum particles having the particle size of 50 ⁇ m were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 1500°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre-sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 1 MPa at 1500°C. The filling ratio of the conductive member was 96%.
  • the average particle size of platinum particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of platinum particles was 50 ⁇ m.
  • the activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics.
  • the volume resistivity p of the conductive member was 1 x 10 5 ⁇ cm.
  • the activation energy Ea was 0.2 eV.
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • Silver particles having the particle size of 0.5 nm were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 2 MPa at 800 0 C. The filling ratio of the conductive member was 96%. [ 0101 ]
  • the average particle size of silver particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of silver particles was 0.5 nr ⁇ .
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200°C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics. The volume resistivity p of the conductive member was 1 x 10 8 ⁇ cm. The activation energy Ea was 0.3 eV. [0103]
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • the beam movement magnitude ⁇ L was 3% or less (0.03L or less) . That is, when the temperature difference was 8°C or less, display images were good.
  • the temperature difference between the face plate and rear plate was 3°C or less, the beam movement magnitude ⁇ L was 1% or less (0.01L or less) . That is, when the temperature difference was 3°C or less, display images were particularly good.
  • Silver particles having the particle size of 50 ⁇ m were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was set to 10.
  • Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a mold while providing vibration.
  • a conductive member was produced by sintering the mold in an Ar gas atmosphere under pressure of 1 MPa at 800°C. The filling ratio of the conductive member was 96%.
  • the average particle size of silver particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of silver particles was 50 ⁇ m.
  • the activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics.
  • the volume resistivity p of the conductive member was 1 x 10 5 ⁇ cm.
  • the activation energy Ea was 0.2 eV.
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • the temperature difference between the face plate and rear plate of the image display apparatus using the spacer was 20°C or less, no beam movement magnitude ⁇ L was detected. That is, when the temperature difference was 20°C or less, display images were good.
  • Gold particles having the particle size of 50 ⁇ m were prepared as powder of conductive particles.
  • the mixture was pre-sintered by heating the mixture at 800°C.
  • Mixed powder was produced by crushing a mixed solid body obtained after the pre- sintering. By classifying the mixed powder, mixed powder called coarse particles whose particle size is 500 ⁇ m and that called fine particles whose particle size is 50 ⁇ m were obtained.
  • the particle size ratio of coarse particles to fine particles was s.et to 10. Coarse particles and fine particles were compounded in the mass ratio of 7:3 and the compounded mixed powder was filled into a forming die while providing vibration.
  • a conductive member was produced by sintering the forming die in an Ar gas atmosphere under pressure of 1
  • the average particle size of gold particles dispersed in the conductive member was determined by using a TEM or SEM.
  • the average particle size of gold particles was 50 ⁇ m.
  • volume resistivity of the conductive member was measured by applying the predetermined electric field (1000 V/mm) after placing the conductive member in a vacuum. While measuring resistance, the conductive member was heated up to 200°C and then, cooled to the room temperature. Resistance temperature characteristics were thereby measured together. The activation energy Ea was determined from an Arrhenius plot of the resistance temperature characteristics. The volume resistivity p of the conductive member was 1 x 10 5 ⁇ cm. The activation energy Ea was 0.2 eV. [0112]
  • a spacer was formed for an image display apparatus using surface conduction electron-emitting devices.
  • an image evaluation of measuring the beam movement magnitude ⁇ L by the influence of the spacer was performed.
  • the material, size or the like may be changed when appropriate.
  • glass whose volume resistivity is 10 14 ⁇ cm is used as an insulating base material.
  • the insulating base material is not limited to this. Any insulating base material may be used when volume resistivity of the spacer is equal to 10 5 ⁇ cm or more. Because an insulating base material is combined with conductive particles, the insulating base material may be appropriately selected from insulating materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
  • Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)

Abstract

La présente invention concerne un élément conducteur pouvant être produit à moindre coût et présentant d'excellentes caractéristiques de température de résistance, une entretoise constituée de l'élément conducteur et un appareil d'affichage d'image utilisant l'entretoise. Plus précisément, l'élément conducteur d'après la présente invention est un élément conducteur comprenant un matériau de base et des particules conductrices, dont la conductivité est supérieure à celle du matériau de base, dispersées dans le matériau de base, et les particules conductrices sont dispersées dans le matériau de base d'une manière telle que l'énergie d'activation de l'élément conducteur est égale à 0,3 eV ou moins et que la résistivité de volume de l'élément conducteur est égale à 105 Ωcm ou plus.
PCT/JP2008/058232 2007-04-23 2008-04-22 Elément conducteur WO2008133338A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08740917A EP2143113A1 (fr) 2007-04-23 2008-04-22 Elément conducteur
US12/282,378 US20100231114A1 (en) 2007-04-23 2008-04-22 Conductive member, spacer made of the conductive member, and image display apparatus

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2007-112533 2007-04-23
JP2007112533 2007-04-23
JP2008-095107 2008-04-01
JP2008095107A JP2008293960A (ja) 2007-04-23 2008-04-01 導電性部材とこれを用いたスペーサ、及び画像表示装置

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WO2008133338A1 true WO2008133338A1 (fr) 2008-11-06

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EP0784326A2 (fr) 1996-01-11 1997-07-16 E.I. Du Pont De Nemours And Company Composition pour conducteur à couche épaisse flexible
JPH10284286A (ja) 1997-04-07 1998-10-23 Canon Inc 帯電防止膜およびその成膜方法及び画像表示装置
EP1090959A1 (fr) 1999-10-06 2001-04-11 Shin-Etsu Chemical Co., Ltd. Composition conductrice de caoutchouc de silicone
JP2001143620A (ja) 1999-02-25 2001-05-25 Canon Inc 電子線装置用スペーサの製造方法と電子線装置の製造方法
US6494757B2 (en) 1999-02-25 2002-12-17 Canon Kabushiki Kaisha Manufacturing method of spacer for electron-beam apparatus and manufacturing method of electron-beam apparatus
EP1333079A1 (fr) 2002-02-01 2003-08-06 Delphi Technologies, Inc. Matériau adhésif conducteur contenant des particules conductrices liées de façon métallurgique
WO2003073543A2 (fr) 2002-02-26 2003-09-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Membrane electrolyte souple a base d'un support comprenant des fibres polymeres, procede de production et utilisation de cette membrane
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US6403209B1 (en) * 1998-12-11 2002-06-11 Candescent Technologies Corporation Constitution and fabrication of flat-panel display and porous-faced structure suitable for partial or full use in spacer of flat-panel display
DE10030838A1 (de) * 1999-07-05 2001-01-11 Luk Lamellen & Kupplungsbau Verfahren zur Versorgung eines eine Getriebesteuerung aufweisenden Automatik-Getriebes und Automatik-Getriebe
EP1998355A3 (fr) * 2004-01-22 2009-02-25 Canon Kabushiki Kaisha Film antistatique, espaceur l'utilisant et unité d'affichage d'images
US7449827B2 (en) * 2004-12-09 2008-11-11 Canon Kabushiki Kaisha Spacer structure for image forming apparatus
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JP4920925B2 (ja) * 2005-07-25 2012-04-18 キヤノン株式会社 電子放出素子及びそれを用いた電子源並びに画像表示装置および情報表示再生装置とそれらの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5236631A (en) 1991-01-31 1993-08-17 Shin-Etsu Chemical Co., Ltd. Rubber composition for anisotropically electroconductive membrane
EP0784326A2 (fr) 1996-01-11 1997-07-16 E.I. Du Pont De Nemours And Company Composition pour conducteur à couche épaisse flexible
JPH10284286A (ja) 1997-04-07 1998-10-23 Canon Inc 帯電防止膜およびその成膜方法及び画像表示装置
JP2001143620A (ja) 1999-02-25 2001-05-25 Canon Inc 電子線装置用スペーサの製造方法と電子線装置の製造方法
US6494757B2 (en) 1999-02-25 2002-12-17 Canon Kabushiki Kaisha Manufacturing method of spacer for electron-beam apparatus and manufacturing method of electron-beam apparatus
EP1090959A1 (fr) 1999-10-06 2001-04-11 Shin-Etsu Chemical Co., Ltd. Composition conductrice de caoutchouc de silicone
EP1333079A1 (fr) 2002-02-01 2003-08-06 Delphi Technologies, Inc. Matériau adhésif conducteur contenant des particules conductrices liées de façon métallurgique
WO2003073543A2 (fr) 2002-02-26 2003-09-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Membrane electrolyte souple a base d'un support comprenant des fibres polymeres, procede de production et utilisation de cette membrane
US20050130024A1 (en) 2003-12-10 2005-06-16 Jsr Corporation Proton conductive composition and proton conductive membrane

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